@article{Peng2023, 
author = {Junchen Peng and Dandan Dong and Zongyuan Wang and Hong Yang and Dongyang Qiao and Qinqin Wang and Wei Sun and Minmin Liu and Jiajun Wang and Mingyuan Zhu and Bin Dai and Fei He and Chaofeng Huang},
title = {Manipulating micro-electric field and coordination-saturated site configuration boosted activity and safety of frustrated single-atom Cu/O Lewis pair for acetylene hydrochlorination},
year = {2023},
journal = {Nano Research},
volume = {16},
number = {7},
pages = {9039-9049},
keywords = {acetylene hydrochlorination, Lewis pair, single-atom Cu, site configuration, electric field},
url = {https://www.sciopen.com/article/10.1007/s12274-023-5681-3},
doi = {10.1007/s12274-023-5681-3},
abstract = {Simultaneously boosting acetylene hydrochlorination activity and avoiding formation of explosive copper acetylide over Cu-based catalyst, which represented a promising alternative to Hg-based and noble metal catalysts, remained challenging. Herein, we fabricated a frustrated single-atom Cu/O Lewis pair catalyst (Cu/O-FLP) by coupling epoxide group (C–O–C) with atom-dispersed Cu-cis-N2C2Cl center to address this challenge. The basic epoxy site modulated the electron-deficient state of Lewis-acidic Cu center and paired with the Cu-cis-N2C2Cl moiety to preferentially break HCl into different electronegative Cu–Clδ− and C–O–Hδ+ intermediates, which further induced both an extra localized electric field to polarize acetylene and a upshift of the d-band center of catalyst, thereby promoting adsorption and enrichment of acetylene by enhancing the dipolar interaction between acetylene and active intermediates. Moreover, the generated Cu–Clδ− and C–O–Hδ+ drastically reduced the energy barrier of rate-limiting step and made vinyl chloride easier to desorb from the Lewis-basic oxygen-atom site rather than traditional Lewis-acidic Cu center. These superiorities ensured a higher activity of Cu/O-FLP compared with its counterparts. Meanwhile, preferential dissociation of HCl endowed single-atom Cu with the coordination-saturated configuration, which impeded formation of explosive copper acetylide by avoiding the direct interaction between Cu and acetylene, ensuring the intrinsic safety during catalysis.}
}